Oil compositions



Patented June 7, 1938 William H. Butler, Palisades Park, N. J., assignor to Bakelite Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 22, 1936, Serial No. 117,149

12 Claims. (Cl. 134-26) The present invention relates to oil composiwhereas comparable coating compositions withtions modified by theaddition of resins of the out the addition of unmodified phenolic resins phenolic type. require about twice the time to dry to print-free V The problem of preparing oil compositions in films and then the films are not as resistant to which phenolic resins are included has occupied. alkalies. I

the attention of many since the time of Berends Rapidity of drying of fatty oils can be propatents which were granted as early as 1916 (see moted by blowing or oxidizing the oils/ Oxidized Patents Nos. 1,191,390 and 1,205,081); according or blown oils are usually prepared by passing a to these patents a phenolic resin is modified by stream of air through a drying oil at temperathe addition of rosin or other natural resin in tures above 150 0. giving heavy liquids with vis- 1o sumcient amount, 1. e. in major proportion, such cosities ranging from 1500 k. v. to 12,500 k. v. that the resin becomes oil-soluble but charac- Blown oil films still require from four to five teristic properties of the phenolic resin, such as days unless driers are included when, they can be hardening under the action of heat, become deso ,speeded up as to dry or become casehardstroyed and the modified resin acts like a novolak ened in from 18 to 20 hrs. Driers, however,

in that it no longer sets up under the action of causea surface drying or hardening of films and heat. Novolak resins, by which are meant resins do not materially accelerate hardening or gelawhich do not set up or harden under the action tion beneath the surface to set the oil to a firm, ofheat to form useful products, are in general homoge eous, rigid e throughout its entire oil-soluble if run in oil at varnish cooking temmass. peratures of 500-600 F. The resins and crystal- A blown or oxidized oil can be heated at eleline bodies of the saliretin type formed by the vated temperatures to bring about an increase in reaction of a phenol with sufllci'ent alkali to form viscosity and cause a certain amount of surface a material amount of a phenate and this in turn skinning; y no appreciable gelatlon takes P reacted with' formaldehyde (generally in large For instance, blown fish oil and blown linseed oil excess over molecular proportions) at low temafter heating in bulk for 16 hoursat 135 C. reperatures are known to be oil soluble. Substimained heavy Viaeous q w n cooled tuted phenols with three or more carbon atoms room temperature K in the ring substituents form resins with form- Ac rdin to t present'invention blown r aldehyde which can be brought into solution with d ed 0118 can be p y p y d to fatty oils without adding modifying agents, and her-like s ids n a y t ss, and a d stinthe greater the number of carbon atoms in the guis'hing characteristic 0 uc gelled Products 15 radicals substituted for the hydrogen of the t at t y a fi m es s a t masses, exhibitin phenol ring the more readily do the resins pre- 110 Surface c hardening but having a ni m pared from them go into solution with fatty oils; hardness iihicfl-lgholiii-v h is accomplished y the heat-hardening property of such resins h including in the blown oils phenolic resins which made under usual operating conditions is, h are oil-soluble and in addition have a reactivity ever, in inverse ratio to the solubility in oils, and u d r th a ti of heat such t at y s t fin or the higher substituted phenols by the procedure harden from a fusible or meltable state to a state commonly followed give resins which for pracwhere they do not melt bu y sof Without tical purposes are not heat-hardening in oils. flowing Within 01,16 to ten minutes d e a ly For association withloil-soluble resins of thewithin two to nvem t Si ca phenolic typeg'as described above, drying and be tested by spreading a small portion as a film semi-drying fatty oils have been used, Inpartlcon a plate heated t0'l60 C. and noting the time ular those resins made from substituted phenols interval required hardening: and without modification by rosin or other nat- The P pa a 0! the resins Suitable o this ural resins markedly improve the character of invention are found to depend p the s Of films deposited by oil compositions containing basic substances limited in amount to catalytic them both as to speed of drying and as to' lk li -proportions (one-fifth of a mol'. or less based on resistance; this action is believed due to an accelthe phenol) and preferably in amounts not 5 erating eilect of the resin on the polymerization greater than 2 parts by weight of ammonium of drying oils. For example, coating compositions hydroxide (or equivalent amounts of other bases) have been prepared from substituted phenol for each parts' of the phenol; the basic subresins and drying oilswhich dry and harden in stances serve to direct the reaction between the from 1 to 4 hours to a film resistant to alkalies, phenol with formaldehyde or equivalent meth ylene-containing agent added in equimolecular or point where the resins are hard or brittle when cold and have a melting point at or above 50 C. In order to prepare compositions of resin and blown oil converted to highly polymerized, rubberlike solids, it is preferred to disperse the resin, while still in the fusible state, into the blown oil I and then heat the oil-resin dispersion at a tem-.

perature of about 100-150 C. for about 2 to 4 hours, when the composition will have set to a soft rubbery gel; the heating may be continued until the composition is converted into a dry soft gel. This procedure can be varied particularly to hasten the gelation of resin-blown oil composition, by first heating the blown oil to somewhat higher temperature of 150 to 260 C. for from 30 to minutes, then dispersing the heat-reactive resin in the hot oil and continuing the heating for 10 to 20 minutes more; this will usuallybe suflicient .to convert the resin-blown oil composition to a rubbery, viscous, mass but of a consistency permitting the incorporation of fillers and pigments.

The proportions of resin and oil can be varied within rather wide limits, for as little as .one part of resin in 20 parts of blown oil having been found to be useful in accelerating the polymerization of the oil; the maximun; amount of resin usually used is 2 parts of resin to 1 of oil. The rapidity at which the composition will gel or set up depends both on the nature of the resin and of the oil. Thus, a resinv which can be converted to the non-melting state, say in five minutes at 160? C., will have a greater accelerating effect than a resinwhich is converted to the nonmelting state in 10 minutes at the same-temperature; in general, however, those resins'which can be converted to the non-melting state within less than 10 minutes at 160 C. have proven the most satisfactory.

Practically any -blown oil can be converted into tough, rubbery-like gels when heated with these reactive resins, although the rapidity of their conversion to the gel state varies with the different oils and the processing to which they have been-subjected. Thus, the polymerization of a composition of blown tung oil and resin as herein defined can be accelerated to 'such an extent by the action of the resins that it solidifies to a soft gel, even at room temperature. The gelled tung oil and resin composition remains comparatively soft, however, even when heated; whereas .a gelled blown fish oil-resin composition has greater firmness and mechanical strength.

Using 50 parts of a heat-reactive resin preparedfrom high boiling tar acid and formaldehyde and 50 parts of blown oil, the 'gelation rate of a number of different oils has beenv determined by measuring the hardness of the resulting gels obtained by heating the'oil-resin' composition for 2 hours at C. and then 2 hours more at 122 C. The results are shown in the following table:

on Shore hardness Firm, hard gel.

Firm 861.

For comparison, a similar experiment was conducted but substituting in one case a natural masses, in floor covering compositions, etc.; that,

is, in uses whichrequire composition masses of considerable thickness.

The gelation of the blown oil-resin composition can be arrested by the addition of appropriate thinners, and in this way dispersions are obtained of reactive blown oil-resin compositions which are suitable for impregnating compounds, wire coating compositions, etc. Such dispersions are generally highly reactive and deposit thick films which gel rapidly throughout their entire mass and which are free of any surface skinning or hardening. Driers or other oxidation accelerating agents are not required, since these films dry by virtue of the polymerization accelerating effect.imparted by the heat-reactive resin. This permits the application of films of considerable thickness (over .002") which dry uniformly and thus effect considerable saving in time, since very often a coating of the requisite thickness to give complete protection can be applied in one operation whereas several coats of the conventional sition may be subjected to a baking operation if a coating of greater stability and resistance is desired; moreover, such baked films will be of uniform hardness and resistance throughout their mass. Due to this uniformity of hardening, it is possible to bake films of greater thickness than is ordinarily the case and yet avoid any tendency to blistering, case hardening, wrinkling or like difficulties such as are normally encountered when thick coatings of the ordinary oil varnishes are applied. I

It has also been found that in many cases it is .not necessary to-heat the blown oil and reactive resin together; instead, it is sumcient to subject the blown or oxidized oils to a preliminary heat treatment, for example, 1 hour at 250 to 300 C., and then cold blend with such heat treated oils a solution of heat-reactive resin in a suitable. solvent such as toluol or xylol. The resulting solution can be used either for coating or impregnating and deposits on evaporation of the solvent a thickfilm of heat-reactive resin dispersed in heat treated blown oil, which can be completely hardened throughout its mass by heating for 1 to 2 hours at to C. This heating stepmay in certain cases be omitted and it is feasible to effect a gelatin of the heat-reactive resinblown oil compositions even at room temperaure. This is, particularly true if the oil used is blown China-wood oil. In this case it has'been found that by allowing a solution of a simple mixture of a heat-reactive resin with the blown China-wood oil to stand at room temperature for a few hours, a gelled composition will result.

In order to more clearly indicate the type of materials obtained by the incorporation of heatreactive resin with blown or oxidized oils, the following typical examples are given.

Example 1. 100 parts of high boiling phenolic compound, of which about 25% has a boiling point range of 225 to 235 C., 30% a range of 235 to 240 0., and a range of 240 to 250 C., is reacted under a reflux with 100 parts of formaldehyde, 37% solution, and 1 part of hexamethylenetetramine for 3 hours at atmospheric pressure. The resin layer is separated and dehydrated by heating-to a-temperature of 110 C. in approximately 1 hour at 100 mm. pressure. The resulting resin is brittle, light amber in color, softens between -100 C. and can 'be polymerized in a layer one mil thick to a state in 50-400 seconds where it does not soften at or below 160 C.

To 200 parts of blown soya bean oilhe ated to 150 C. and the heat then removed, are added 100 parts of resin prepared as above described. The addition-of resin causes the .temperature to drop to about 100 C. in 3 minutes and this temperature is maintained for about another 10 minutes. The resulting composition is a viseous liquid, having a viscosity of about 1000 k. v., it.

is heat-reactive and it can be further polymerized to a firm gel by heating for 2 hours at 135 C. Thinned with appropriate solvents it may be used as an impregnating varnish or as a wire enamel. This type of coating, after baking, has improved resistance to solvents such as mineral spirits and aromatic hydrocarbons.

Example 2.'200 parts of blown linseed oil are brought to 'a temperature of 260 C. in 40 minutes and held at this temperature five minutes. The partially polymerized blown oil is then cooled to 100 C;, 100 parts of resin prepared as in Example 1 are then added, and the resin-oil composition is held 10 to 15 minutes at 100 C. The resulting viscous liquid composition, having a viscosity of about 2000 k. v., is heat-reactive. It may be further polymerized if desired, to a -iirm gel by heating for 1 hour at 135 C;,"the

polymerization proceeding uniformly throughout the mass without wet spots or surface skins ning. For coil impregnation and the like it may be thinned. with appropriate solvents such as mineral spirits, aromatic hydrocarbons and the like.

Example 3.500 parts of biown linseed oil are brought to a temperature of 260 C. in 40 minutes and held at'this temperature for 25 min utes. The partially polymerized blown oil is then combined with 100 parts of resin made according to Example 1. The resulting viscous composition, having a viscosity of about 600 k. v.,

, polymerizes to a soft gel when heated, 3 to 5 hours at 135 C. It maybe used as an impregnating compound for brake lining and the like, either with or[ without the addition of thinners.

Example 4.-100 parts of an oil soluble heathardenable phenolic resin made.v according to Example 1 is dissolved in 60 parts of toluol; 100

parts of brown China-wood oil are then mixed with the resin solution at 20 to 25 C. Such a resin-oil composition will gradually polymerize to atsolid over a period of three to five hours at a temperature'of 24-30 C.

Another .composition, in which 3 parts of blown China-wood oil and' l-part of heat-reactive resin are admixed at a low temperature, is sufiiciently liquid to be cast into a mold, as for example, a mold for a printing roll. When baked at 100 C. for about 4 hours a soft rubbery composition, re-

sistant to gasoline and water, is obtained which proves'satisfactory as a printing roll. I 7 Example 5.100 parts of para tertiary amyl phenol is reacted with 150 parts formaldehyde,

37% solution, under a reflux with 10 parts of 20% caustic solution for approximately 1 hour. The

reaction mixture is cooled, acidified with dilute sulphuric acid and theresin layer extracted with toluene. The resin solution is then washed, the toluene distilled off, and the resulting, product is a light colored, hard, brittle, oil-soluble and heat-hardenable resin that is of slower reactivity ,than the resin of Example 1 and softens at about C. It can be compounded with blown oil, for instance by kneading '150 parts of blown linseed oil, 150 parts of blown fish oil and sheeted on rolls and used as such for calendercoating; or it can be extruded directly over metallic conductors to give them a flexible resistant coating. Ifa somewhat softer composition is desired itissometlmes advantageous to add about 10% of a plasticizer, such astricresyl phosphate, at the time the fillers are incorporated.

In the above example para-phenyl phenol can be substituted in whole or in part in about the same proportions to give a resin of substantially the same properties. V Y

Example 6.-A brittle, heat-r tive and oilsoluble resin-is prepared'by refluxing 100 parts of para butyl phenol with 150 37% formaldehyde solution and 1 part barium hydroxide until resin separation occurs. reaction mixture is then subjected to under diminished pressure until a hard, brittle resin is obtained, when a test sample is into water at 25 C. The resultinsrsain is light colored andsoftens at about l5to 80 C. 100 parts of this resin are kneaded with 300' parts of blown fish oil at a temperature of to 160 C. for about 4 hours, or. until the composition has polymerized to a soft gel. Atthls point fillers, such as asbestine, clay, wood flour, cotton flock and the like, in the proportion of 1 part fillerto 4 parts blown oil-resin composition are added along with suitable pigment, such as carbon black. titanium oxide, or suitable dyes. One or two per cent of a catalyst, such as litharge or a methylene-containing agent as, for example, hexamethylenetetramine or paraform which further accelerates the gelling, can be included.

The kneading of theresin and oil composition can be continued at.120 C. for another 2 hours or until the comp tion is ,converted to a dry, rubbery mass whi can be sheeted on rolls. 100 parts of this material are then compounded with 100 parts of a fusible phenolic formaldehyde resin, that is; a novolak, and 100 parts of wood flour, and this is milled-on differential rolls, heated to 80 to C. for about 5 minutes or until a thorough mixing of the ingredients is obtained. On cooling, the brittle mass is ground to pass a 10 mesh screen and about 10 parts of this material are compounded with 90 parts of a molding mixture prepared from equal parts of the usual potentially reactive phenol-form-.

pressure and a temperature of 160 C. and discharged hot at the end of 1 minutes; yet it possesses about more flow than a similar molding mixture containing none of the blown oil, heat-reactive resin composition.

' Example 7.150 parts of blown fish oil, 150 parts of blown soya bean oil, 100 parts of resin prepared as in Example 1 are kneaded together at 120 to 160 C. for, about 2 to 3 hours or until the composition has polymerized to a dry, soft gel. 5 to 10. parts of the resulting-material are compounded with 'to parts of a potentially heat-reactive phenolic resin wood flour molding mixture to give a molding compound of f 40 to 50% increased flow, yet heat-hardenable in a standard molding cycle of 3 minutes at 150 C.

Example .8.Blown linseed oil is heat-treated by heating to 290 C. during a course of 50 minutes. The oil is cooled to 25 C. 300 parts of this heat treated blown oil are reheated to 175 C., the heat removed and parts of heat-reactive resin, prepared as in Example 1, are added and the mixture agitated until the resin has completely dispersed in oil. The temperature is then raised to 175 C. and then suiilcient xylol added to give a solution containing 70% solids. This solution may be used as an impregnating compound.

Example 9.100 parts of heat-reactive resin, prepared as in Example 1, are dissolved by refluxing in 100 parts of xylol. This resin solution is mixed with 300 parts of 'blown linseed oil, heat treated as in Example 8. The resulting solution can be used as an impregnatingcompound; for example, asbestos fiber such as used in brake linings may be impregnated and the impregnated lining hardened by heating to a temperature of C. or higher for 1 to 2 hours, when polyr merizationoi the binder is effected.

Example 10.500 parts blown linseed oil are partially polymerized by heating to 260 C. during a course of 30 minutes and then held at this temperature for 1% hours. It is then cooled to C. and 100 parts of resin, made as in Example 1, are then dispersed in this partially polymerized oil, this operation requiring about 5 to 10 minutes. Immediately after the resin has been thus dispersed, the mixture foams due to reaction of resin splitting ofl' water and becomes more. and more viscous and is completely polymerized in 10 to 20 minutes at 150 C. This .material' is a rubbery viscous mass but of a consistency to permit the incorporation of fillers and pigments. Such a composition is particularly adapted for the production of linoleum,

' without requiring the long time usually required for the hardening of linoxyn.

Example 11 .A composition suitable i'or floor covering is made according to Example 10, except 2000 parts of the partially polymerized blown linseed oil are combined with 100 parts of the heat-reactive oil-soluble resin. The resin is combined with the partially polymerized blown linseed oil and reacted in akneader for 2 to 6 hours at 120 to C. or until the mixture has polymerized to a soft rubbery mass. Fillers or pigments can then be incorporated and the corona effect of high tension currents; as soften- Dispersions of these blown oil-heat-reactive resin compositions in suitable solvents form highly. efiective impregnating compounds, since the heat-reactive character of the composition is retained "in such dispersions, thus making it possible to impregnate fabrics for use in brake linings, in electrical insulation, to impregnate 'wood and similar porous'substances'and then subsequently subject the impregnated object to heat. Thisresults in a material which is impregnated with completely polymerized oil-resin binder which is free of surface oxidation and which retains its toughness and pliability almost indefinitely.

The blownoll-resin dispersions may also be used as coating compositions,"and the film deposited will be tough and-free of the objectionable aging characteristics common to rubber and to oil-resin compositions polymerized in the presence of siccative agents.

What is claimed is:

1. Process oi preparing a composition convertible by heating to a rubber-like gel which comprises forming an oilsoluble heat-reactive condensation product of a phenol withan aqueous aldehyde in equimolecular orgreater proportions and in the presence'oi not more than one-fifth mol. of a basic catalyst, said condensation. product being in an intermediate stage of and a reactivitysuch as to set to a state where it does not melt at 160 C. when heated for a .thousandths of an inch.

2. Process according to claim 1 in which the phenol has a hydrocarbon radical as a substituent in the ortho or para position. I

3. Process according to claim 1 in which the phenol is a tar acid fraction having a boiling point ranging from 225 C to 250 C.

4. Process according to claim 1 in which the basic catalyst is present in amount equivalent to not more than two parts of ammonium hydroxide to 100 parts of phenol.

5. Process according to claim 1 in which the blown oil is subjected to a preliminary heat treatment.

6. Process according to claim 1 in which the resin is blended with the blown oil by means 01' heat. I

'7. Composition convertible to .a rubber-like gel comprising in combination a blown oil and an oil-soluble heat-reactive condensation product of a phenol with an aqueous aldehyde in equimolecular or greater proportions and in the presence.

' of not more than one-fifth mol. ofa basic cata- 1 lyst, said condensation product being in an intermediate stage of reaction with a melting-point at or above 50 C. and a, reactivity, such as to set to a statewhere it does not melt at 160 C. when heated for a period of from one to ten minutes, said resin and said oil being blended in the proportions of from about two parts of the resin with from one to forty parts of the reaction with a melting point at or above 50 C.

blown oil, and said composition in the converted gel form being characterized by a uniformity of hardness in film thicknesses in excess of two-- thousandths of an inch.

8. Composition according to claim 7 in which the phenol has a hydrocarbon radical as a substituent in the ortho or para position.

9. Composition according to claim 7 in which the phenol is a tar acid fraction having a boiling point ranging from 225 C. to 250 C.

10. Composition according to claim 7 in which the basic catalyst is present in amount equivalent to not more than two parts of ammonium hydroxide to 100 parts of phenol. 

